Polyalkenamers and process for the preparation thereof

ABSTRACT

Polyalkenamers are produced by a ring-opening polymerization of cyclic olefins employing a catalyst containing a tungsten or molybdenum compound and conducting the polymerization in the presence of an ethylenically unsaturated halogenated hydrocarbon wherein one of the double bonded carbon atoms is substituted by chlorine, bromine or iodine or halogenated alkyl or aryl and at least one hydrogen atom.

United States Patent 1 1 Streck et a1.

I POLYALKENAMERS AND PROCESS FOR THE PREPARATION THEREOF 751 Inventors:Roland Streek; Heinrich Weber,

both of Marl, Germany [73] Assignee: Chemisehe Werke lluelsAktiengesellschaft, Marl, Germany 22 Filed: June 11, 1971 [21] Appl.No.:152,373

[30] Foreign Application Priority Data June II, 1970 Germany 2028716[52] US. Cl.. 260/677 R, 260/666 A, 260/683.15 R

[51] Int. Cl. C07c 11/00 [58] Field of Search 260/677, 666 A, 683.15,260/683 D [56] References Cited UNITED STATES PATENTS 3,045,001 7/1962Berger 252/4291; 3,159,014 12/1964 Bloyaertetal 252/4291;

[451 June 11, 1974 3,530,196 9/1970 Singleton .1 260/680 3,535,40110/1970 Calderon et a1. 260/683 3,634,539 1 H1972 Alkema et al. 260/6833,637,893 1/1972 Singleton 260/683 D 3,647,908 7/1972 Medema et al.260/683 D FOREIGN PATENTS OR APPLICATIONS 2,006,777 2/1970 France260/680 R Primary Examiner-Delbert E. Gantz Assistant Examiner-JuanitaM. Nelson Attorney, Agent, or Firm-Millen, Raptes & White 57 ABSTRACT 23Claims, No Drawings POLYALKENAMERS AND PROCESS FOR THE PREPARATIONTHEREOF BACKGROUND OF THE INVENTION This invention relates to a processfor the preparation of polyalkenamers by the ring-opening polymerizationof cyclic olefins employing a catalyst containing a metal of Subgroups 5through 7 of the periodic table or a compound thereof and to novelpolyalkenamers thusproduced.

It is known that cyclic olefins containing at least one unsubstitutedring double bond can be polymerized under ring-opening conditions. Thecatalysts employed for this ring-opening polymerization are supportedcatalysts which contain a metal of Subgroups 5 through 7 of the periodictable, or the compounds thereof. See German Published Application DASNo. 1,072,81 1. Preferred catalysts are the reaction products ofcompounds of the above-mentioned metals with organometallic compounds orhydrides of metals of Main Groups 1 through 3 or Subgroup 2 of theperiodic table, as well as optionally compounds which contain one ormore hydroxy and/or sulfhydryl groups. See French Pats. Nos. 1,394,380and 1,467,720; the published disclosures of Dutch Patent applicationsNos. 65-10,331; 66-05,l05; 66-l4,413; 67-O4,424; 68-06,208; and 68-06,21l. The catalysts described therein contain compounds of molybdenum ortungsten and, as organometallic compounds, usually organoaluminumcompounds. According to the published texts of Dutch Patent applicationsNos. 67-l4,559 and 68-06,209, vanadium, niobium, tantalum, rhenium,technetium, or manganese can also be components of such catalystsystems.

In accordance with German Unexamined Published application DOS No.1,909,226, it is also possible to employ catalyst systems containing ahalide or an oxyhalide of molybdenum or tungsten wherein the stage ofoxidation of the metal is 4, 5 or 6, an aluminum trihalide.

With the aid of these catalysts, a great variety of polymers can beprepared with structures which are strictly regular along thepolymerchains, the structure of the polymer units being exclusivelydependent on the cycloolefin employed as the monomer. Thus, it ispossible, for example, to produce linear polymers by the polymerizationof monocyclic olefins; polymers having recurring polymer unitscontaining a single ring by the polymerization of bicyclic olefins; and,in general, polymers having recurring polymer units which contain onering less than the starting monomer by the polymerization of polycyclicolefinsl The polyalkenamers produced by the polymerization of monocyclicolefins are of particular interest for the additional reason that,depending on the cycloolefin employed, it is possible to preparepolymers having differing double bond content. Thus, polybutenamerswhich are free of vinyl groups, i.e., pure 1,4- polybutadienes, areobtained from cyclobutene, 1,5 cyclooctadiene, and1,5,9-cyclododecatriene. Polypentenamers are obtained from cyclopentenewhich have three -CH -groups disposed between the double bonds.Polyoctenamers are produced from cyclooctene which correspond to acompletely regular semihydrogenated l,4-polybutadiene. Polydecenamersare prepared from cyclododecene correspondong to a twothirdshydrogenated 1,4-polybutadierie in which refects properties of thepolymer and thus its usefulness in any particular field of application,as well as its characteristics during the production and processing.Thus,

polymer solutions of equal weight concentration of polymer are moreviscous, the higher the molecular weight of the polymer in solution.Thus,.difficulties are encountered with solutions of very high-molecularpolymers, e.g., during the polymerization, for example, in the mixing orobtaining satisfactory heat exchange, and increased energy requirementsfor the agitating step result. Also, the further processing of veryhighmolecular polymers is difficult. For this reason, they are oftendegradated mechanically, chemically, or thermally prior to the finalshaping procedure, e.g., injection-molding, extrusion, or calendering.

The polyalkenamers obtained during the ringopening polymerization of.cycloolefins are normally very high-molecular. Because of theabove-described difficulties with polymers of very high molecularweight, attempts have been made in the prior art to develop processesfor regulating the molecular weight of the polymers producible by agreat variety of polymerization methods. In the polymerization ofa-olefins with organometallic mixed catalysts, the so-called hydrogenregulation, i.e., polymerization in the presence of a certain partialhydrogen pressure, proved useful. Other possibilities for controllingthe molecular weight of a-olefin polymers were varying the catalystcomponents, elevating the temperature or adding alkylzinc oralkylcadmium compounds during the polymerization.

Although organometallic mixed catalysts or related catalyst systems arealso employed in the ring-opening polymerization of cycloolefins, themethods for molecular weight regulation employed in the polymerizationof the a-olefins either are unsuccessful or exhibit definitedisadvantages which make the use of such methods difiicult, if notimpossible. Thus, hydrogen, for example, up to an excess pressure of 4atmospheres exerts practically no influence at all on the molecularweight of the polyalkenamers prepared by the ring-opening polymerizationof cycloolefins. Even if hydrogen were effective at pressures higherthan those mentioned above, the hydrogen regulating method would requireincreased investment costs, since the plant would have to be designedfor pressures which do not occur in the unregulated ring-openingpolymerization of the cycloolefins which, under normal pressure, arepresent in the liquid phase or in solution at the polymerizationtemperature. Although the molecular weight of the polyalkenamers can bereduced by employing a higher polymerization temperature, the yield andthe steric uniformity of the polymers are impaired in so doing.Moreover, due to the temperature sensitivity of the mixed catalystscustomarily employed for the ringopening polymerization of cycloolefms,such catalysts become inactive above 40-50 C. in a short period. Also,modifications of an optimal catalyst system can strongly impair yield.See, for example, Dutch Patent application No. 66-O5,l05, p. 16.

The last of the above-mentioned methods for controlling the molecularweight during the polymerization of a-olefins with organometallic mixedcatalysts, i.e., using an alkylzinc or alkylcadmium compound as thecontrolling agent, is of little practical use, even if it were efiectivein the ring-opening polymerization of cycloolefins, because such zincand cadmium compounds are very toxic and can be prepared only withdifficulty and thus are expensive.

The only process heretofore known wherein polymers are obtained whichexhibit improved processability is described in British Patent No.1,098,340. In this process, cyclic monoolefins are copolymerized underring-opening in the presence of a conjugated diolefin, such as, forexample, butadiene, isoprene, or 1,3- pentadiene. The thus-producedcopolymers contain polymer units derived from both the cycloolefin andthe conjugated diolefin, in varying molar ratios.

As shown in Comparative Experiments N through T in Table 3, conjugateddienes, although they influence the molecular weight of thepolyalkenamers produced in polymerizations conducted in their presence,also are more or less strong catalyst poisons. Thus, for example, thepresence of only 1 mol% of 1,3-butadiene, 5 mol% of isoprene, 5 mol% of2,3-dimethyl-l,3- butadiene, or mol% of 2,4-hexadiene, results in thecomplete inhibition of the polymerization catalyst and no polymer isobtained. Cyclic conjugated diolefins also cause a pronounced loweringof the yield of polymer. Moreover, it is not possible using such dienesas polymerization regulators to produce polymers which are waxy oroil-like products having very low molecular weights, i.e., about5005,000.

In our prior application Ser. No. 70,497 filed Sept. 8, 1970, we-claim aprocess for the regulation of molecular weight of polyalkenamers by theaddition of monoolefins, preferably a-olefins, during thepolymerization. The molecular weight of polyalkenamers can be regulatedwith a very high degree of success by this process. However, there is agreat interest in polymers having functional terminal groups, which canbe employed for further reactions, such as, for example, cross-linkingreactions or for the construction of other defined polymer structures,e.g., block copolymers or stellate polymers. For example, a stellatestructure is obtained by the reaction of a unilaterallylithium-terminated polymer, e.g., a polybutadiene or polystyreneproduced in a polymerization which employs butyllithium as the catalyst,with a trior tetrahalogen compound, such as, for example,methyltrichlorosilane, silicon tetrachloride, or carbon tetrabromide. Achain of a polymer terminating at both ends in halogen can be reactedwith a unilaterally metal-terminated chain of another polymer to formblock copolymers. Polymer chains terminating in hydroxyl groups can becross-linked with di-, tri-, or polyisocyanates or other polyfunctionalcompounds, such as, for example, acid chlorides of polybasic acids.These examples are typical but not complete and merely illustrate thatsuch reactions of telechelic polymers" (US. Pat. No. 3,244,664) havegained in creasing importance in recent times. Functional end groupsalso often influence the practical application properties of thepolymers and effect, for example, an

improved adhesion to surfaces and/or an improved compatibility withother polymers. Thus, there is an increasing need for processes yieldingpolymers having defined functional end groups.

Accordingly, it is an object of the present invention to provide aprocess which makes possible, in a simple manner, to simultaneouslyregulate the molecular weight of polyalkenamers produced by theringopening polymerization of cyclic olefins and to introduce functionalterminal groups into the polymer molecule. Another object is to providenovel polymers thusproduced. Other objects will be apparent to thoseskilled in the art to which this invention pertains.

SUMMARY OF THE INVENTION According to this invention, the molecularweight of polyalkenamers produced by the ring-opening polymerization ofcyclic olefins employing a catalyst containing a metal of Subgroups 5 to7 of the periodic table and conducting the polymerization in thepresence of an ethylenically unsaturated halogenated hydrocarbon whereinone of the double bonded carbon atoms is substituted by chlorine,bromine or iodine or halogenated alkyl, cycloakyl, aryl or alkaryl andat least one bears a hydrogen atom.

DETAILED DISCUSSION The cyclic olefin and cycloolefin employed in theprocess of this invention are unsaturated hydrocarbons containing one ormore rings, at least one of which contains at least one unsubstitutednon-conjugated double bond.

The cycloolefins polymerized according to the process of this inventionpreferably contain four to 12 ring carbon atoms and a total of four to20, preferably four to 15 carbon atoms; from one to three, preferablyone to two rings, which can be fused or separate cycloaliphatic rings;whose ring carbon atoms are unsubstituted or one or more of which aresubstituted with loweralkyl, e.g., of one to four carbon atoms,cycloalkyl, e.g., of five to seven carbon atoms, or aryl, alkaryl oraralkyl, e.g., of six to ten carbon atoms.

Preferred classes of starting cycloolefins are the following:

a. those containing one to two non-conjugated double bonds, preferablyone;

b. those containing one to two rings, preferably one;

c. those of (a) and (b) containing two fused rings;

d. those of (a), (b), and (c) containing 0-2 loweralkyl groups as thesole substituents on the ring carbon atoms, preferably 0;

e. those of (d) containing l2 methyl groups as the sole substituents onthe ring carbon atoms;

f. those of (a), (b), (c), (d), and (e) wherein the unsaturated carbonatoms each bear a hydrogen atom; and

g. those of (a), (b), (c), (d), (e) and (f) wherein the ring of thecycloolefin containing the unsaturation contains five or seven to 12ring carbon atoms.

Examples of cycloolefins which can be polymerized according to theprocess of this invention are cyclobutene, cyclopentene, cycloheptene,cyclooctene, cyclononene, cyclodecene, cycloundecene, cyclododecene,cis, cis-l,5- cyclooctadiene, I-methyl-1,5- cyclooctadiene, 3,7-dimethyll ,S-cyclooctadiene, 1,5,9-cyclododecatriene, 4,5-dimethyl-l,4,7- cyclodecatriene, cis,trans- 1 ,S-cyclodecadiene, norbornene,dicyclopentadiene, dihydrodicyclopentadienc. and 4-phenylcyclooctene,and mixtures thereof. Cycloolefins which cannot be polymerized withring-opening,

e.g., cyclohexene and the derivatives thereof, are not employed asstarting monomers in the polymerization process of this invention.

The polymerization of this invention is conducted in the presence, as apolymerization regulator, of an unsaturated halogenated hydrocarbon asdefined herein. These compounds can be represented by the formulawherein R, R and R" are hydrogen, chlorine, bromine, iodine, alkyl,cycloalkyl, aryl, alkaryl or the corresponding halogenated groups, atleast one of R, R and R" being a halogen atom or halogenated alkyl,cycloalkyl, aryl or alkaryl but no more than one of R, R and R" being ahalogen atom. For example, R, R and R" can be straight-chain or branchedsaturated alkyl of one to 20, preferably one to 12, carbon atoms, orcycloalkyl containing three to 12, preferably five to 12 ring carbonatoms, one, two or three separate or fused rings,'and three to20,-preferably five to 12 carbon atoms, unsubstituted or substituted byone or more halogen atoms. Examples of aryl are those containing six to14 carbon atoms and one, two or more separate or fused rings,unsubstituted or substituted by unsubstituted or halogenated alkyl orcycloalkyl as defined above. 7

Examples of alkyl are methyl, ethyl, propyl, isopropyl, butyl, isobutyl,tert.-butyl, hexyl, heptyl, octyl and higher straight and branched chainalkyl. Cycloalkyl includes cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, 2-methyl cyclopentyl, 2,6-dimethylcyclopentyl,4-methylcyclohexyl, 3,5-dimethylcyclohexyl, 2- methylcyclohexyl,cycloheptyl, cyclooctyl, octohydronaphthyl, and the corresponding groupssubstituted on one or more ring carbon atoms by alkyl of one to fourcarbon atoms. Aryl includes phenyl, p-diphenyl, naphthyl, ar-loweralkyl,e.g., p-benzylphenyl, benzyl, phenethyl, 2-phenyl propyl and benzhydryl;tetrahydronaphthyl, 6-tetrahydronaphthyl indenyl, dihydroindenyl.Alkaryl includes aryl substituted on one or more ring carbon atoms byalkyl of one to four carbon atoms, preferably methyl, e.g., p-tolyl,sym.-xylyl, etc.

Especially preferred are monohalogenated aliphatic a-olefins substitutedonly on a double bonded carbon atom by a single chlorine, bromine, oriodine atom,

e.g., vinyl chloride, vinyl bromide, vinyl iodide, pro--dibromobutene-2, l l-chloroundecenel 5- bromopentenel 5-chloropentenel4-chlorobutene-. l, 1,6-dichlorohexene-3, 1,6-dibromohexene-3, 1,8-dichloroctene-4, 1,8-dibromoctene-4, and 3,4- dichlorobutenel Theunsaturated halogenated hydrocarbons can be utilized as the purecompounds or in the form of mixtures, e.g., the halogenated mixtureswhich are very inexpensively produced in various petrochemicalprocesses, for example during the high-temperature chlorination ofolefins or the chlorination or hydrochlorination of diolefins.

When a halogenated olefin is employed as the regulator which issubstituted only on one side of the double bond by halogen, e.g., vinylchloride, the resulting polymers possess, on the average, onehalogen-containing end group per macromolecule. However, macromoleculescan also be produced which have no halogencontaining end group at all orwhich have two halogencontaining end groups. Macromolecules with twohalogen-containing end groups are always obtained when using controllingagents which are halogenated'on both sides of the double bond, forexample, 1,4- dibromobutene-2, 1,6-dichlorohexene-3, l-chloro-7-bromoctene-3, p,p-dibromostilbene, or

o-fluorol -chlorallybenzene.

A surprising peculiarity of the monohalogenated aliphatic a-olefinssubstituted only on the double bond by chlorine, bromine, or iodine isthat they exert, even in very small quantities ranging in the order ofmagnitude of catalyst concentration, a favorable influence on thevelocity and yield of the polymerization, in addition to controllingmolecular weight. This activator effect cannot be explained by means ofany of the heretofore known theories regarding the mechanism of theringopening polymerization of cyclic olefins.

With the aid of these activators, it is also possible to developcatalyst systems based on tungsten hexachloride and ethylaluminumsesquichloride or diethylaluminum chloride, which normally exhibit onlyminor catalytic activity, which are highly satisfactory polymerizationcatalysts. Ethylaluminum dichloride containing catalysts, which haveheretofore shown the highest activity, is manufactured in smallerquantities than the two other above-mentioned ethylaluminum halogenidesand, moreover, can be handled only in dilute solutions, due to itsmelting point of +32 C. Furthermore, catalysts containing ethylaluminumdichloride have a strong tendency to promote secondary reactions of acationic type. Thus, for example, they have an alkylating effect onaromatics and polymerize branched olefins, which can result in gelling.

By employing the activating regulators or regulating activators of thisinvention, a considerable increase in catalyst activity is alwaysattained, even in the case of catalysts containing ethylaluminumdichloride, so that high conversion rates can be obtained, even when thepolymerization is conducted in dilute solutions, which reactionordinarily progresses very unsatisfactorily, especially in case ofcyclopentene. This is also advantageous from the viewpoint of processtechnique, for it is possible to polymerize a higher proportion of themonomer rather than being forced, as in case of bulk polymerization, toutilize the monomer as the solvent and work with small conversions, dueto the viscosity of the thus-produced polymer solution, and toregenerate and recycle the larger portion of the monomer. Besides,especially in the case of cyclopentene, the polymerization need nolonger be conducted at the very uneconomical low temperatures of -20 to--30 C. Instead, the same or even still higher yields are obtained underconditions which are technically and economically more advantageous to20 C.).

The ring-opening polymerization of cyclic olefins can be conducted byconventional procedures employing known catalysts. Thus, suitablecatalysts are supported catalysts containing the metal of Subgroupsthrough 7 of the periodic table, for example, in the form of thecarbonyl, sulfide, or superficially reduced oxide on a support such as,for example, aluminum oxide, aluminum silicate, or silica gel. Alsosuitable are mixed catalysts, e.g., containing a compound of a metal ofGroups 5 through 7 of the periodic table and an organometallic compoundor hydride of a metal of Main Groups 1 through 3 or Subgroup 2 of theperiodic table and optionally, also a compound containing one or morehydroxy and/or sulfhydryl groups. Also suitable are catalysts containinga halide or oxyhalide of molybdenum or tungsten wherein the degree ofoxidation of .the metal is 4, 5, or 6, and which contain an aluminumtrihalide. Preferably, mixed catalysts are employed containing amolybdenum compound or especially a tungsten compound. Preferredorganometallic compounds are organolithium, organomagnesium andorganoaluminum compounds, especially methylaluminum dichloride,ethylaluminum dichloride, methylaluminum sesquichloride, ethylaluminumsesquichloride, dimethylaluminum chloride and diethylaluminum chloride.Compounds containing one or more OH- and/or SH-groups optionally can beemployed concomitantly as a catalyst component, e.g., water, hydrogensulfide, hydroperoxide, alkyl hydroperoxides, mercaptans,hydrodisulfides, alcohols, polyalcohols, polymercaptans andhydroxymercaptans. Saturated and unsaturated alcohols and phenols, viz.,n-propanol, n-butanol, sec.- butanol, isobutanol, allyl alcohol, crotylalcohol, phenol, o-m m, and p-cresol, 0: and ,B-naphthol, eugenol andbenzyl alcohol, especially methanol, ethanol, isopropanol, ortert.-butanol, are preferred. However, when employing an activatingregulator according to this invention, compounds containing Ol-land/orSH- groups offer only minor advantages and can be omitted.

The polymerization can be conducted continuously or discontinuously. Thereaction temperature can vary widely, e.g., between 70 C. and +50 C.However, temperatures between 30 and +30 C. are preferred.

The amount of regulator which is added and, as a consequence, themolecular weight of the polymers produced, can be varied widely withoutany disadvantageous effects on the yield and the stereospecificity ofthe polymerization. When employing, for example, cyclobutene orcyclopentene as the monomer, it is thus possible to produce rubber-likeproducts of a high The amount of regulator needed to attain a product ofa specific consistency depends, inter alia, on the type of the monomeremployed, the type of regulator employed, the catalyst employed, and theselected polymerization reaction conditions. The exact amount ofregulator can readily be determined by a few preliminary experiments.

The amount of unsaturated halogenated hydrocarbon employed can vary fromabout 0.001-50 molar percent, based on the monomer. Generally, the useof about 0.00l-5, preferably about 0.003-5, more preferably about 0.01-5mol-percent, and more preferably about 0.01-2 mol-percent, based on themonomer employed, results in the production of polyalkenamers havingmolecular weights in the range of commercial elastomersortherrnoplastics. The addition of between about 7 and 50 molar percent,preferably between about 10 and 20 mol-percent of the regulator, basedon the monomer employed, generally is required for the production oflow-viscosity to oily products.

These data apply when using regulators which do not simultaneouslyincrease the polymerization velocity and the polymer yield. In contrastthereto, when using activating regulators, about one-tenth of the abovequantities often is sufficient for the preparation of polyalkenamershaving molecular weights in the range of commercial elastomers orthermoplastics.

Since the activating effect of the monohalogenated aliphatic a-olefinswhich are substituted only on the double bond by a single chlorine,bromine or iodine atom is clearly perceptible with the addition of avery small amount thereof, e.g., approximately 1 molar percent of theheavy metal component of the catalyst, especially in case of tungstencompounds and particularly in case of tungsten hexachloride, theseactivating regulators can also be considered to be components of thecatalyst system and can be employed primarily for the purpose ofimproving yield. Any desired reduction of the molecular weight of thepolymer lower than would be obtained with the use of these additives bythemselves, can be achieved by the additional use of other regulators,for example the previously proposed a-olefins. This combination ofactivating regulators and a-olefins is particularly advantageous whenvery lowmolecular products are to be manufactured, e.g., oils, and noimportance is attributed to functional end groups of the polymer becausesuch end groups would not offer any special advantage for the intendedpurpose for which the products are to be used.

The polymerization process of this invention is preferably conducted insolution. For this purpose, inert solvents inert under the reactionconditions are employed, e.g., benzene, cyclohexane, methylcyclohexane,isopropylcyclohexane, Decalin, hydrogenated kerosene, paraffin oil,methylene chloride, trichloroethylene and preferably hexane, heptane,octane, and perchloroethylene. The amount of solvent employed can varywidely, e.g., 5 to 2,000 percent by weight, preferably 50 to 1,000percent by weight, based on the monomer employed. Low-molecular oilypolymers can also advantageously be prepared without a solvent by masspolymerization, so long as the viscosity of the thus-reacted mixtureremains reasonably low.

The amount of catalyst which need be employed is very low. For example,in case of tungsten hexachloride, only about 0.5 2 millimols per literof reaction volume, or about 1 mol per 1,000 5,000 mols of monomer, isrequired. When using an activating regulator, this quantity can bereduced to approximately onetenth the amount, in spite of the improvedyield. The concentration of organometallic catalyst component dependsprimarily on the purity of the monomer and the solvent employed, i.e.,the amount of moisture, peroxides, proton-active impurities, such asalcohols, acids, and other compounds reacting with alkyl metals, such asethers, amines, ketones, aldehydes, etc., present therein. When themonomer and the solvent are subjected to a very thorough preliminarypurification and the reactants are handled with strict exclusion of airin thoroughly dried reactors, molar ratio of heavy metal compound toactive alkyl metal, i.e., an alkyl metal which has not been bound ordestroyed by impurities many additional additives present, of about 1:4to 1:1, preferably less than lzl, is generally sufficient. Outside ofthis range, the catalysts are normally less active.

As in the case of regulating the molecular weight of polyalkenamers withmonoolefms, surprisingly it is not necessary in the process of thisinvention that the regulator be present at the beginning of thepolymerization in order to obtain the desired effect. The regulator can,if desired, be added after polymerization has begun. All that isrequired is that the catalyst is still active, i.e., the regulator mustbe added prior to the inactivation of the catalyst. It is thus possibleto use regulators which tend to form homopolymers which are insoluble inthe reac tion mixture if exposed to the catalyst, either by themselvesor in a mixture with cycloolefins at the beginning of thepolymerization, and thus inactivate the catalyst by inclusion in theinsoluble polymer, or which enter into secondary reactions with thecatalyst components prior to the actual formation of the catalyst, butwhich do not react in such a manner with the finished catalyst. Thetendency of a regulator to promote homopolymerization or enter into suchsecondary reactions can quickly be determined by preliminaryexperiments. Because of this characteristic, it is also possible when anunforeseen rise in the viscosity of a polymerization batch takes place,as occasionally happens, to keep the contents of the kettle stirrable byadding the regulator before inactivation of the catalyst, thus avoidingthe extensive work connected with emptying a batch which sulfhydrylgroups.

Preferred aspects of the catalyst systems of this invention comprise oneor more of any of the following:

a. component 1 is tungsten hexachloride or tungsten oxytetrachloride;

b. component 2 is an alkyl aluminum halide, preferably ethylaluminumdichloride, ethylaluminum sesquichloride or diethylaluminummonochloride;

c. component 3 is vinyl chloride, vinyl bromide and- /or vinyl iodide;

d. the molar ratio of component (I) to component (2) is less than 1 z 1,preferably between 1 l and l 50;

e. the molar ratio of component (1) to component (3) is less than 1,preferably less than 10 l;

f. the molar ratio of component (l) to component (4) is about 1 10.1 tol 2; and/or g. the molar ratio of component l to the difference of theamounts employed of component (2) minus component (4) is between about l1 and l 4.

After the termination of the polymerization reaction, the polyalkenamerscan be isolated and purified in a conventional manner. If thepolyalkenamers are obtained in solution or in the liquid phase, theresidues of the catalyst can be removed with an alcohol or othercompound having an acidic hydrogen, by washing out thepolymer-containing phase with an aqueous or aqueous-alcoholic solutionof agents having a dissolving ef feet on the catalyst residues, whichlatter are first presout as an alcoholate or a salt of the othercompound having an acidic hydrogen atom used to remove the catalysLSuchsubstances with a dissolving effect on the catalyst are, for example,acids, bases, or complexfonning agents, such as acetylacetone, citric ortartaric acid, ethylenediaminetetraacetic acid, 'nitrilotriacetic acid,etc.

After the catalyst has been removed, the polymers are separated byprecipitation, e.g., by pouring into a precipitant such as, for example,methanol, isopropanol, or acetone,'or distilling off the solvent, e.g.,by blowing in steam, or by introducing the polymer solution throughnozzles into hot water. When the polymer can be precipitated from thesolution of the monomer in the form of flakes or a powder, the polymercan first be separated, e.g., by filtration, centrifuging, or decantingfrom the liquid and thereafter treated to remove the catalyst residues.

In order to protect the polyalkenamers against oxidation, gelling, andother aging phenomena, it is possible to add stabilizers thereto, e.g.,aromatic amines or the sterically hindered phenols, at various stages ofprocessing. Also, an optional further purification step can be conductedby reprecipitating the polymer if this should be necessary, to obtain aproduct of the desired purity. After these operations, the polymer canthen be dried in a conventional manner.

In contrast to the previously known polyalkenamers which, althoughcalled linear polymers, in reality, are macrocyclic compounds, thepolyalkenamers prepared in accordance with the process of this inventionare truly linear polymers of a strictly regular structure with exactlydefined terminal groups. Such polymers have not heretofore beenproduced.

The polyalkenamers produced in accordance with the process of thisinvention are, in contrast to the polymers known heretofore whichalthough called linear polymers are in reality macrocyclic compounds,true linear polymers of a strictly regular structure with exactlydefined end groups, which have not been described heretofore.

By the ring-opening homopolymerization according to the process of thisinvention of monocyclic monoolefins of the general Formula I polymersofthe general Formula II are obtained:

LR. J.

wherein in both instances R ishydrogen or a straightchain or branchedsaturated alkyl of l to 6 carbon atoms, saturated cycloalkyl of 3 to 6carbon atoms or aryl of 6 to 10 carbon atoms, and X, m and y have thevalues given below.

The various o Rr the molecule can be alikeordifferenu ie, can be IIIwherein X, y andm have the val ues given below. 7 i 7 By thering-openinghomopolymerization of monocywherein, in Formulae IV and V, X, y and havethe values given below, and R R R and R which are alike or different,have the same value as R Thus, R and/or R groups can be disposedthroughout the polymer molecule. In other words, n of the R groupsand/or 0 of the R can be hydrogen or I to n of the R groups and/or 1 too of the R groups can also be alkyl or aryl, respectively. The sameapplies to R and/or R groups, which likewise can both be hydrogen oreither or both can also be identical or different alkyl or aryl groups.Thus, by the ring-opening homopolymerization of unsubstituted monocyclicdiolefins of Formula IV wherein R R R, and R are hydrogen, there are obtained polymers of the general Formula VI.

X={=CH (CH2), CH CH (CH=)., CHQETX 12 are produced by the ring-openingpolymerization of monocyclic triolefins of the general Formula VIII 12VIII wherein X and y have the values given below and R R R R Rm, R and Rwhich can be alike or different, have the same values as R The various RR and/or R groups can be identical or different groups.

i.e., all p of the R groups, all q of the R groups and/or all r of the Rgroups can be hydrogen; or from 1 to p of the R groups, I to q of the Rgroups and/or 1 to r of the R groups can, respectively, be an alkyl oraryl group. The same is true of the R R R and/or R which likewise canall represent hydrogen, or individually or severally, can be identicalor different alkyl or aryl groups.

Homopolymers of the general Formula VII X: CH-((I3H C=(]i(ClH (]3-Cl3-on 4:112:21 L R; 1: I11 Ra Ra q R10 11 R12 0 1 VII By the ring-openinghomopolymerization of norbornene there are obtained polymers of thegeneral Formula IX.

wherein X and y have the values given below.

Polymers containing two or more of the abovedescribed polymer units in astatistical distribution or in larger block sequences are producedduring the ringopening copolymerization of two or more of theabovedescribed cycloolefins in the presence of the claimedpolymerization regulators.

In Formulae II, III, V, VI, VII and IX, m is the integer 2 or 3 or aninteger from 5 to l0 inclusive; n and 0 each integers from 1 to 7, thesum of which is an integer from 3 to 8; p, q, and r each are the integerl or 2; and y is an integer from 2 to about 50,000, preferably 5 toabout 20,000.

The novel polyalkenamers of this invention are characterizedstructurally by their novel terminal groups. These groups are alkylideneradicals derived from the ethylenically unsaturated halogenatedhydrocarbon employed in the polymerization as the polymerizationregulator. Thus, in Formulae II, III, V, VI, VII and IX, X is C3 IX,(Angew. Chem. 76, 765 1964) and J. Pol. Sci. 6, 2405 (1968) thatpolyalkenamers prepared by ring-opening polymerization of cycloolefinshave strictly linear structure. Later on Calderon alleged that thosepolyalkenamers are in reality macrocyclic compounds (J. Am. Chem. Soc.90, 4l33 (1968)). This proposition was proved by isolation andidentification of macrocyclic oligomers with polymerization rates up tol 1 (Adv. Chem Ser. 91, 399 (1969)).

The novel polyalkenamers can unexpectedly and readily be worked up, asthey have a lower reduced melt viscosity. Therefore they may be workedup by lower temperature, e.g., by calendering, rolling or injectionmoulding, whereby the energy-costs are much smaller.

Without further elaboration, it is believed that one skilled in the artcan, using the preceding description, utilize the present invention toits fullest extent. The following preferred specific embodiments are,therefore, to be construed as merely illustrative, and not lim- 14polymer was then precipitated by pouring the organic phase into 3 litersof methanol. The precipitated product was dissolved once again in 250ml. of hexane, for purposes of an additional purification, andreprecipitated with methanol to which was again added 2 g. of stabilizer(IONOL). After decocting the polymer for 2 hours with 500 ml. of puremethanol, it was dried for 40 hours at 50 C. in a vacuum drying chamber.The thus-purified polymer was employed for determining the yield and theanalytical data. In each case, such a blank test (designated in thetable by capital letters) was conducted to exclude sources of errors dueto changing impurities in the solvent, the monomer, or the catalystcomponents, in parallel to the polymerizations employing one of threeregulator olefins (numbered examples). The regulators to be tested wereadmixed with the monomers in the examples. In Table 1, the amount TABLE-1 Polymerization of cyclopentene (100 ml.=77.8 g. per experiment) inhexane (150 ml. per experiment). Catalyst system: 0,5 millimol oftungsten hexachIoride/0.5 millimol of ethanol/changing amounts ofethylaluminum dichloride.

Polymerization temperature: C. Polymerization time. 2.5 hours.

Regulator Polymer EtAlCl in the Amount RSV Trans Experiment catalyst(mol Yield (d1. content Gel Number (mmol) percent) Name (g.) lg.)(percent) (percent) 4 0. 1 Vinyl acetate 12. 8 l. 8 90 2 4 0. 1 AlIylacetate 16. 2 3. 0 81 4 14. 4 1. 0 Vinyl propionate.. 40. 9 1. 8 74 325. 8 1. 0 Methylvinyl adipate 31. 7 2. 9 66 8 25. 8 1. 0 Diallylsuccinate 19. 8 2. 5 82 22 14. 4 1. 0 Vinyl stearate 40. 0 1. 0 81 8 14.4 1. 0 Octadecen-(Q) -yl acetate 19. 7 1. 7 74 4 14. 4 1. 0 Methyloleate l8. 2 2.0 84 7 14. 4 l. 0 Allyl chloroacetate 34. 6 0.82 l 7 14.4 1. 0 Ally] dichloroacetate 22. 4 0. 77 ca. 100 14 25.8 1.0 Diallylphthalate 21.7 1.55 73 2 15.4 1. 0 Buten-(1)-yl-3-acetat 27. 4 1. 28 912 25. 8 1. 0 Divinyl adipate" 48. 5 1. 03 81 4 15. 4 1. 0 Vinylisobutyrate 47. 0 0. 91 76 3 itative of the remainder of thed'i'ci'siir' in any Way whatsoever. Unless stated otherwise, the reducedspecific viscosity (RSV) and the gel contents were determined in benzeneat C.

EXAMPLES l-l2 AND COMPARATIVE EXPERIMENTS A-E lnto a three-tube l-literglass flask with agitating unit and reflux condenser with a droppingfunnel attached thereto were introduced, respectively, 100 ml. (77.8 g.)of Cyclopentene and 150 ml. of hexane and were brought under anatmosphere of extremely pure nitrogen, to the reaction temperature bycooling or heating, and are mixed with the components of thepolymerization catalyst. After the predetermined reaction period, thecatalyst was destroyed by the addition of ml. of methanol containing 3g. of potassium hydroxide and. 2 g. of 2,6-di-tert.-butyl-p-cresol(IONOL). After the addition of 100 ml. of distilled water and 50 ml. ofmethanol, so that a second phase containing 50 percent methanol wasformed, the reaction mixture was then further agitated for 3 hours, towash out the catalyst residues. The aqueousmethanolic phase was thenremoved by pipetting and the reaction mixture was washed twice with 50percent aqueous methanol. The

of regulator]; set forth in molar percent, based on the monomeremployed.

50 Ml. (38.9 g.) of Cyclopentene and 50 ml. (42 g.) of cyclooctene werediluted with l50 ml. of hexane and cooled to 0 C. Then 0.5 millimol oftungsten hexachloride, 0.5 millimol of ethanol, and 3 millimols ofethylaluminum dichloride, and 5 millimols of vinyl bromide were addedthereto under agitation. After 2.5 hours, the catalyst was decomposed inthe manner described in Examples l-l2. The polymer was worked up in themanner described therein. There was obtained 58.5 g. of a polymer havingan RSV of 1.9 dl./g. The polymer contained 76.8 molar percent ofpolyoctenamer units (determined by nuclear resonance analysis). 63percent of the double bonds thereof detectable by ultrared spectroscopywas present in the trans-configuration and 37 percent was present in thecis-configuration.

In a comparative experiment wherein the vinyl bromide was omitted, therewas obtained only 2.9 g. of a polymer having reduced specific viscosityof L6 dl./g.

and containing 35.7 molar percent of polyoctenamer units and aproportion of trans-double bonds of 92 percent.

EXAMPLE 14 AND COMPARATIVE EXPERIMENT G Copolymerization of Cyclopenteneand Cyclododecene By replacing the cyclooctene in Example 13 by the samevolume (43.5 g.) of cyclododecene and substituting 10 millimols of vinylchloride for the vinyl bromide, 48.0 g. of a polymer was obtained havinga reduced specific viscosity of 1.3 dL/g. and containing 48.4 molarpercent of polydodecenamer units. 76 percent of the double bonds thereofdetectable by ultrared spectroscopy are in the transconfiguration.

In a comparative experiment in which the vinyl chloride was omitted,only 1.8 g. was obtained of a polymer having a reduced specificviscosity of 1.7 dl./g., a content of polydodecenamer units of 11 molarpercent, and a proportion of trans-double bonds of 82 percent.

It can be seen from Examples 13 and 14, as well as ComparativeExperiments F and G that the polymeriza- A further comparativeexperiment conducted without vinyl bromide wherein the ethylaluminumsesquichloride was replaced by ethylaluminum dichloride resulted in onlya minor increase in yield to 5.8 g.

EXAMPLE 16 Use of Ethylaluminum Sesquichloride Example 15 was repeatedexcept the ethanol in the catalyst system was omitted. There wasobtained 31.7

g. of a polypentenamer with a reduced specific viscosity of 1.4 dl./g.and a gel content of 2 percent with 75 percent of the double bondspresent in the transconfiguration.

Examples 15 and 16 and Comparative Experiments H and J demonstrate thattungsten hexachloride, in combination with ethylaluminum sesquichlorideand vinyl bromide, is a substantially more effective catalyst system forthe ring-opening polymerization of cyclopentene than the combination oftungsten hexachloride with ethylaluminum dichloride and ethanol.

Similar results are obtained with the use of diethylaluminum chloride asthe organometallic component of the catalyst system, the only'difference being that the ti f y l t at 0 C, i tr ly i hibit d b thaddition or omission of ethanol has practically no influsimultaneouspresence of cyclooctene or cyclododecence on the yield in polypentenamerincreased by the ene. However, the addition of vinyl halogenides overuseof vinyl bromide (39.4 g. or'40.0 g. in batches recomes this inhibitionnad makes possible the producacted in accordance with Examples 15 and16). tion of copolymers in high yield.

EXAMPLE 15 AND COMPARATIVE EXAMPLES I7-25 AND COMPARATIVE EXPERIMENTS HAND J EXPERIMENTS K-M Use of Ethylaluminum Sesquichloride Polymerizationof Various Cycloolefins 100 ml. (77.8 g.) of cyclopentene was dilutedwith Examples 17-25 and Comparative Experiments K-M 150 ml. of hexaneand cooled to 0 C. Thereafter, 0.5 were conducted as described inExamples l-l2 and millimol of tungsten hexachloride, 0.5 millimol ofetha- Comparative Experiments A-E. The solvent was tech nol, 3 millimolsof ethylaluminum sesquichloride, and nical hexane in all cases (boilingpoint limits: 68-70 5 millimols of vinyl bromide 'were added underagita- C.). The amount of the solvent was selected so that the tion.After a reaction time of 2.5 hours, the catalyst was 40 solutions, priorto the polymerization, contained 20 decomposed in the manner describedin Examples percent by volume of cyclooctene or cyclododecene, ll2.Working up the polymer in the manner disclosed or 10 percent by volumeof 1,5-cyclooctadiene. therein, there was thus obtained 13.8 g. of apolypente- The polymerizates were worked up as described namer having aRSV of 1.2 dl./g. and a gel content of above and then analyzed.

' TABLE 2 Polymerization of various cycloolcfins.

Catalyst system: 0.5 mmol tungsten hexachloride/0.5 mmolethanol/changing amounts of ethylaluminum dichloride.

Polymerization temperature: 20 C.

Regulator Polymer EtAlClz lolymcriin the lotion RSV Trans- GelExpericatalyst time Mol- Yield ((11. content (permcnt No. Monomer M]. G.(mmol) (hours) percent Name (g.) lg.) (percent) cent) v""i'ii1"'1 gas'23 1 v 0.1 my 0 on e 0.0 1. 18"" H Cyclooctene 84 3 0.25 1 d 529 L26 195 .d0 65.9 1.10 1)" "i'tY'i'iii 1U '38 -c oropropene 21.4 1. 21clcmdmecemm- 87 4 25 1.0 1,3-dichloropropne 13.9 1.25 1.0Z-rnethylene-l,3-dichloropropane... 9.0 1.07 M" 63.8 2.05 g2;1,5-cyclooctadiene. 100 87.7 3 0.25 3:3 25 10 do 70.7 1.05

Nort:.ln Examples 17 through 22 and Comparative Experiments K and L, theRSV-values were measured in 1)ecalin" at C.

less than 2 percent. Of the double bonds detectable by ultraredspectroscopy, 77 percent were present in the 65 trans-configuration.

In a comparative experiment in which the vinyl bromide was omitted, only2.8 g. of polymer was obtained.

COMPARATIVE EXPERIMENT SERIES N-T (See Table 3) Comparative ExperimentsN-T were conducted in the manner described for Examples l-I 2 andComparative Experiments A-E. For each experiment, 100 ml.' (87.5 g.) ofcyclododecene were employed as the monomer and 150 ml. of technicalhexane (boiling point limits: 6870 C.) were employed as the solvent. Thevarious conjugated dienes were utilized in varying amounts. The molarpercent of diolefins set forth in Table 3 refers, in each case, to thecycloolefin employed. For each experiment there was em-ployed as thecatalyst millimol of tungsten hexachloride, 0.5 millimol of ethanol, and3 millimols of ethylaluminum dichloride. In all experiments thepolymerization time was 2.5 hours at 20 C. The polymerizates were workedup in a manner described above and then analyzed.

v bon atoms.

6. A process according to claim 1 wherein the unsaturated halogenatedhydrocarbon is vinyl chloride, bromide or iodide.

7. A process according-to claim 1 wherein the unsat- TABLE 3 PolymerExperiment Conjugated series diolefin Mol- Yield RSV, Trans, number namepercent g. Percent d1./g. percent N 1,3-butadiene 21. 9 25. 2 1. 96 40 1O. 8 0. 9 C. 30 40 5 0. 2 0. 2 0. 06 10 0. 3 0. 3 0. G7

0 Isopreue 46. 1 53. 0 2. 25 46 1 47. 1 54. 2 1. U7 44 2 10. l 11. 6 0.94 52 5 No Polymer P 2,3-dimethylbutadiene 21. 6 24. 8 2. 45 1 12. 0 13.8 1. 46 5 No Polym r Q, 2,4-hexadiene 37. 8 43. 5 2. 22 49 1 24.9 28.6'0.47 40' 5 7. 2 8. 3 0. 15 42 10 No Polym r R Cyclopentadiene 45. 4 52.32. 26 52 s 1,3-cyclododecadiene- 47. 2 54. 2 2. 16 43 1 13. 9 16. 0 1.02 42 5 1. 8 2. 1 10 1. 5 1. 7

T 1,3-cycl0octadiene 2s. 5 a0. 5 1. 63 41 1 12. 2 14. 0 1. 61 36 5 8. 19. 3 1. 52 46 10 4. 0 4. 6 1. 1C 43 1 Too little substance.

2 Polymer contains insoluble components.

Nora-A11 RSV-values were measured at 135 C. in De-calm."

The preceding examples can be repeated with similar success bysubstituting the generically or specifically described reactants and/oroperating conditions of this invention for those used in the precedingexamples.

From the foregoing description, one skilled in the art can easilyascertain the essential characteristics of this invention, and withoutdeparting from the spirit and scope thereof, can make various changesand modifications of the invention to adapt it to various usages andconditions.

What is claimed is:

1. A process for the production of polyalkenamers by the catalyzedring-opening polymerization of cyclic olefins employing a ring-openingcatalyst comprising a tungsten an molybdenam compound which comprisesconducting the polymerization in the presence of an ethylenicallyunsaturated halogenated hydrocarbon wherein one of the double bondedcarbon atoms is substituted by chlorine, bromine or iodine orhalogenated alkyl, cycloalkyl, aryl or alkaryl and at least one of whichbears a hydrogen atom.

2. A process according to claim 1 wherein the cyclic olefin ismonocyclic, monounsaturated and contains four, live or from seven to 12ring carbon atoms or is monocyclic, diunsaturated and contains fromseven to 12 ring carbon atoms.

molar percent, based on the monomer.

11. A process for the production of syrupy and liquid polyalkenamersaccording to claim 1 which comprises employing as the monomercyclobutene, cyclopentene. cyclooctene, a mixture of cyclobutene andcyclopentene, a mixture of cyclobutene and cyclooctene, or a mixture ofcyclopentene and cyclooctene and employing about 7-50 molar percent,based on the monomer. of the unsaturated halogenated hydrocarbon.

12. A process according to claim ll wherein about lO-20 molar percent,based on the monomer, of the unsaturated halogenated hydrocarbon isemployed.

13. A process according to claim 1 wherein the catalyst is a catalystsystem comprising: (l) a tungsten or molybdenum compound; (2) anorganoaluminum compound; and (3) an ethylenically unsaturatedhalogenated hydrocarbon wherein one of the double bonded carbon atoms issubstituted by chlorine, bromine or iodine or halogenated alkyl,cycloalkyl, aryl or alkaryl and at least one of which bears a hydrogenatom.

14. A process according to claim 13 further comprising: (4). a compoundcontaining one or more sulfhydryl groups.

15. A process according to claim 13 wherein component 1 is tungstenhexachloride or tungsten oxytetrachloride.

16. A process according to claim 13 wherein component 2 is an alkylaluminum halide.

17. A process according to claim 13 wherein component 2 is ethylaluminumdichloride, ethylaluminum sesquichloride or diethyl-aluminummonochloride.

18. A process according to claim 13 wherein compo- -nent'3 isci-ethylenically unsaturated and whose sole halogen substituent is asingle chlorine, bromine or iodine atom on one of the ethylenicallyunsaturated carbon atoms.

19. A process according to claim 18 wherein component 3 is vinylchloride, bromide or iodide.

20. A process according to claim 13 wherein the molar ratio of component1 to component 2 is less than 1 l. g v

21. A process according to claim'13 wherein the molar ratio of component1 to component 3 is less than 100 1.

22. A process according to claim 21 wherein the molar ratio of componentI to component 3 is less than 10 l.

23. A process according to claim 14 wherein the molar ratio of component1 to component 4 is about 1 UNITED STATES PATENT OFFICE CERTIFICATE 'OFCORRECTION Patent No. 3'815'384 Dated June 11, 19 74 I t a1.

It is certified that error appears in the aboVe-identified patent andthat said Letters Patent are hereby corrected as shown below:

IN THE CLAIES:

CLAIM 1, LINE 4 OF THE CLAIM, COLUMN 1?:

"an" should read or and "molybdenam" should read molybdenum Signed andsealed this 29th dayof October 1974.

(SEAL) Attest MCCOY M. GIBSON JR. C. MARSHALL DANN Attesting OfficerCommissioner of Patents FORM PO-IOSO (10-69) USCOMM DC v w u.s.GOVERNMENT PRINTING arm: 1 law o-ass-au,

2. A process according to claim 1 wherein the cyclic olefin ismonocyclic, monounsaturated and contains four, five or from seven to 12ring carbon atoms or is monocyclic, diunsaturated and contains fromseven to 12 ring carbon atoms.
 3. A process according to claim 1 whereinthe unsaturated halogenated hydrocarbon is Alpha -ethylenicallyunsaturated.
 4. A process according to claim 1 wherein both doublebonded carbon atoms bear a hydrogen atom.
 5. A process according toclaim 4 wherein the sole halogen substituent is a single chlorine,bromine or iodine atom on one of the ethylenically unsaturated carbonatoms.
 6. A process according to claim 1 wherein the unsaturatedhalogenated hydrocarbon is vinyl chloride, bromide or iodide.
 7. Aprocess according to claim 1 wherein the unsaturated halogenatedhydrocarbon is added after the polymerization is initiated and beforethe polymerization catalyst is inactivated.
 8. A process according toclaim 1 wherein the amount of unsaturated halogenated hydrocarbonemployed is about 0.001-50 molar percent, based on the monomer.
 9. Aprocess according to claim 8 wherein the amount of unsaturatedhalogenated hydrocarbon employed is about 0.001-5 molar percent, basedon the monomer.
 10. A process according to claim 9 wherein the amount ofunsaturated ether employed is about 0.01-2 molar percent, based on themonomer.
 11. A process for the production of syrupy and liquidpolyalkenamers according to claim 1 which comprises employing as themonomer cyclobutene, cyclopentene, cyclooctene, a mixture of cyclobuteneand cyclopentene, a mixture of cyclobutene and cyclooctene, or a mixtureof cyclopentene and cyclooctene and employing about 7-50 molar percent,based on the monomer, of the unsaturated halogenated hydrocarbon.
 12. Aprocess according to claim 11 wherein about 10-20 molar percent, basedon the monomer, of the unsaturated halogenated hydrocarbon is employed.13. A process according to claim 1 wherein the catalyst is a catalystsystem comprising: (1) a tungsten or molybdenum compound; (2) anorganoaluminum compound; and (3) an ethylenically unsaturatedhalogenated hydrocarbon wherein one of the double bonded carbon atoms issubstituted by chlorine, bromine or iodine or halogenated alkyl,cycloalkyl, aryl or alkaryl and at least one of which bears a hydrogenatom.
 14. A process according to claim 13 further comprising: (4) acompound containing one or more sulfhydryl groups.
 15. A processaccording to claim 13 wherein component 1 is tungsten hexachloride ortungsten oxytetrachloride.
 16. A process according to claim 13 whereincomponent 2 is an alkyl aluminum halide.
 17. A process according toclaim 13 wherein component 2 is ethylaluminum dichloride, ethylaluminumsesquichloride or diethyl-aluminum monochloride.
 18. A process accordingto claim 13 wherein component 3 is Alpha -ethylenically unsaturated andwhose sole halogen substituent is a single chlorine, bromine or iodineatom on one of the ethylenically unsaturated carbon atoms.
 19. A processaccording to claim 18 wherein component 3 is vinyl chloride, bromide oriodide.
 20. A process according to claim 13 wherein the molar ratio ofcomponent 1 to component 2 is less than 1 :
 1. 21. A process accordingto claim 13 wherein the molar ratio of component 1 to component 3 isless than 100 :
 1. 22. A process according to claim 21 wherein the molarratio of component 1 to component 3 is less than 10 :
 1. 23. A processaccording to claim 14 wherein the molar ratio of component 1 tocomponent 4 is about 1 : 0.1 to 1 : 2.